US4349533A - Toothpaste containing pH-adjusted zeolite - Google Patents
Toothpaste containing pH-adjusted zeolite Download PDFInfo
- Publication number
- US4349533A US4349533A US06/217,602 US21760280A US4349533A US 4349533 A US4349533 A US 4349533A US 21760280 A US21760280 A US 21760280A US 4349533 A US4349533 A US 4349533A
- Authority
- US
- United States
- Prior art keywords
- zeolite
- zeolites
- dentifrice
- modified
- pbw
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- 239000010457 zeolite Substances 0.000 title claims abstract description 149
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 title claims abstract description 105
- 229910021536 Zeolite Inorganic materials 0.000 title claims abstract description 91
- 239000000606 toothpaste Substances 0.000 title claims description 17
- 229940034610 toothpaste Drugs 0.000 title claims description 12
- 239000000203 mixture Substances 0.000 claims abstract description 49
- 239000000551 dentifrice Substances 0.000 claims abstract description 40
- 239000002245 particle Substances 0.000 claims abstract description 25
- 238000005498 polishing Methods 0.000 claims abstract description 14
- 238000009472 formulation Methods 0.000 claims abstract description 13
- 239000003082 abrasive agent Substances 0.000 claims description 15
- 239000003795 chemical substances by application Substances 0.000 claims description 15
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 12
- 239000011575 calcium Substances 0.000 claims description 12
- 229910052791 calcium Inorganic materials 0.000 claims description 10
- 238000005115 demineralization Methods 0.000 claims description 9
- 230000002328 demineralizing effect Effects 0.000 claims description 9
- 238000005299 abrasion Methods 0.000 claims description 8
- 239000002002 slurry Substances 0.000 claims description 8
- 239000002253 acid Substances 0.000 claims description 7
- ANOBYBYXJXCGBS-UHFFFAOYSA-L stannous fluoride Chemical compound F[Sn]F ANOBYBYXJXCGBS-UHFFFAOYSA-L 0.000 claims description 5
- 229960002799 stannous fluoride Drugs 0.000 claims description 5
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical compound [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 claims description 4
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 3
- 229910001449 indium ion Inorganic materials 0.000 claims description 3
- 229910052725 zinc Inorganic materials 0.000 claims description 3
- 239000011701 zinc Substances 0.000 claims description 3
- XGRSAFKZAGGXJV-UHFFFAOYSA-N 3-azaniumyl-3-cyclohexylpropanoate Chemical compound OC(=O)CC(N)C1CCCCC1 XGRSAFKZAGGXJV-UHFFFAOYSA-N 0.000 claims description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 2
- 230000018044 dehydration Effects 0.000 claims description 2
- 238000006297 dehydration reaction Methods 0.000 claims description 2
- 229910052749 magnesium Inorganic materials 0.000 claims description 2
- 239000011777 magnesium Substances 0.000 claims description 2
- 230000009467 reduction Effects 0.000 claims description 2
- 239000011775 sodium fluoride Substances 0.000 claims description 2
- 235000013024 sodium fluoride Nutrition 0.000 claims description 2
- 229960000414 sodium fluoride Drugs 0.000 claims description 2
- 229960004711 sodium monofluorophosphate Drugs 0.000 claims description 2
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims 1
- 239000013078 crystal Substances 0.000 claims 1
- 229910052731 fluorine Inorganic materials 0.000 claims 1
- 239000011737 fluorine Substances 0.000 claims 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 14
- 208000002925 dental caries Diseases 0.000 abstract description 9
- 229910000323 aluminium silicate Inorganic materials 0.000 abstract description 7
- 230000015572 biosynthetic process Effects 0.000 abstract description 4
- 230000008719 thickening Effects 0.000 abstract description 2
- 239000010419 fine particle Substances 0.000 abstract 1
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 19
- 239000000463 material Substances 0.000 description 19
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 10
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 10
- 230000009471 action Effects 0.000 description 9
- 235000011187 glycerol Nutrition 0.000 description 9
- 229910052751 metal Inorganic materials 0.000 description 9
- 239000002184 metal Substances 0.000 description 9
- 108090000790 Enzymes Proteins 0.000 description 8
- 102000004190 Enzymes Human genes 0.000 description 8
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 description 8
- 239000003086 colorant Substances 0.000 description 8
- 239000011734 sodium Substances 0.000 description 8
- 235000019333 sodium laurylsulphate Nutrition 0.000 description 8
- 230000000694 effects Effects 0.000 description 7
- 239000000796 flavoring agent Substances 0.000 description 7
- 230000006870 function Effects 0.000 description 7
- 239000004615 ingredient Substances 0.000 description 7
- 239000000843 powder Substances 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- 235000019634 flavors Nutrition 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- 230000004048 modification Effects 0.000 description 5
- 238000012986 modification Methods 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 229910052708 sodium Inorganic materials 0.000 description 5
- 239000000600 sorbitol Substances 0.000 description 5
- 235000010356 sorbitol Nutrition 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 4
- JUNWLZAGQLJVLR-UHFFFAOYSA-J calcium diphosphate Chemical compound [Ca+2].[Ca+2].[O-]P([O-])(=O)OP([O-])([O-])=O JUNWLZAGQLJVLR-UHFFFAOYSA-J 0.000 description 4
- 229940043256 calcium pyrophosphate Drugs 0.000 description 4
- 150000001768 cations Chemical class 0.000 description 4
- 235000019821 dicalcium diphosphate Nutrition 0.000 description 4
- 239000000499 gel Substances 0.000 description 4
- 150000002500 ions Chemical class 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- CVHZOJJKTDOEJC-UHFFFAOYSA-N saccharin Chemical compound C1=CC=C2C(=O)NS(=O)(=O)C2=C1 CVHZOJJKTDOEJC-UHFFFAOYSA-N 0.000 description 4
- 229940081974 saccharin Drugs 0.000 description 4
- 235000019204 saccharin Nutrition 0.000 description 4
- 239000000901 saccharin and its Na,K and Ca salt Substances 0.000 description 4
- 239000000377 silicon dioxide Substances 0.000 description 4
- 230000001225 therapeutic effect Effects 0.000 description 4
- 241000894006 Bacteria Species 0.000 description 3
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 239000011230 binding agent Substances 0.000 description 3
- 239000000872 buffer Substances 0.000 description 3
- 239000001110 calcium chloride Substances 0.000 description 3
- 229910001628 calcium chloride Inorganic materials 0.000 description 3
- 239000002537 cosmetic Substances 0.000 description 3
- 239000012065 filter cake Substances 0.000 description 3
- 235000003599 food sweetener Nutrition 0.000 description 3
- 239000003906 humectant Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000003755 preservative agent Substances 0.000 description 3
- 239000007858 starting material Substances 0.000 description 3
- 239000003765 sweetening agent Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 230000001464 adherent effect Effects 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 239000000969 carrier Substances 0.000 description 2
- 239000008406 cosmetic ingredient Substances 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 210000004268 dentin Anatomy 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 229940091249 fluoride supplement Drugs 0.000 description 2
- 235000013355 food flavoring agent Nutrition 0.000 description 2
- 238000010335 hydrothermal treatment Methods 0.000 description 2
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 2
- 238000005342 ion exchange Methods 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 230000003449 preventive effect Effects 0.000 description 2
- 230000002285 radioactive effect Effects 0.000 description 2
- 230000021317 sensory perception Effects 0.000 description 2
- 229910001415 sodium ion Inorganic materials 0.000 description 2
- 239000002562 thickening agent Substances 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- UBLAMKHIFZBBSS-UHFFFAOYSA-N 3-Methylbutyl pentanoate Chemical compound CCCCC(=O)OCCC(C)C UBLAMKHIFZBBSS-UHFFFAOYSA-N 0.000 description 1
- 229920001817 Agar Polymers 0.000 description 1
- 241000416162 Astragalus gummifer Species 0.000 description 1
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 description 1
- 241000206575 Chondrus crispus Species 0.000 description 1
- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 description 1
- FBPFZTCFMRRESA-JGWLITMVSA-N D-glucitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-JGWLITMVSA-N 0.000 description 1
- 235000019739 Dicalciumphosphate Nutrition 0.000 description 1
- 241000206672 Gelidium Species 0.000 description 1
- 229910003556 H2 SO4 Inorganic materials 0.000 description 1
- 239000004354 Hydroxyethyl cellulose Substances 0.000 description 1
- 229920000663 Hydroxyethyl cellulose Polymers 0.000 description 1
- 239000005909 Kieselgur Substances 0.000 description 1
- 239000004367 Lipase Substances 0.000 description 1
- 102000004882 Lipase Human genes 0.000 description 1
- 108090001060 Lipase Proteins 0.000 description 1
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 description 1
- HDSBZMRLPLPFLQ-UHFFFAOYSA-N Propylene glycol alginate Chemical compound OC1C(O)C(OC)OC(C(O)=O)C1OC1C(O)C(O)C(C)C(C(=O)OCC(C)O)O1 HDSBZMRLPLPFLQ-UHFFFAOYSA-N 0.000 description 1
- 101100386054 Saccharomyces cerevisiae (strain ATCC 204508 / S288c) CYS3 gene Proteins 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- 229920001615 Tragacanth Polymers 0.000 description 1
- -1 Zeolite X Chemical compound 0.000 description 1
- 235000010489 acacia gum Nutrition 0.000 description 1
- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical compound [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000004964 aerogel Substances 0.000 description 1
- 235000010419 agar Nutrition 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- JYIBXUUINYLWLR-UHFFFAOYSA-N aluminum;calcium;potassium;silicon;sodium;trihydrate Chemical compound O.O.O.[Na].[Al].[Si].[K].[Ca] JYIBXUUINYLWLR-UHFFFAOYSA-N 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 229910001424 calcium ion Inorganic materials 0.000 description 1
- 239000001506 calcium phosphate Substances 0.000 description 1
- 108010089934 carbohydrase Proteins 0.000 description 1
- 150000001720 carbohydrates Chemical class 0.000 description 1
- 235000014633 carbohydrates Nutrition 0.000 description 1
- 239000001768 carboxy methyl cellulose Substances 0.000 description 1
- 235000010418 carrageenan Nutrition 0.000 description 1
- 239000000679 carrageenan Substances 0.000 description 1
- 229920001525 carrageenan Polymers 0.000 description 1
- 229940113118 carrageenan Drugs 0.000 description 1
- 229910001603 clinoptilolite Inorganic materials 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000003750 conditioning effect Effects 0.000 description 1
- 239000002178 crystalline material Substances 0.000 description 1
- 230000007123 defense Effects 0.000 description 1
- 210000003298 dental enamel Anatomy 0.000 description 1
- 210000004513 dentition Anatomy 0.000 description 1
- 239000003599 detergent Substances 0.000 description 1
- NEFBYIFKOOEVPA-UHFFFAOYSA-K dicalcium phosphate Chemical compound [Ca+2].[Ca+2].[O-]P([O-])([O-])=O NEFBYIFKOOEVPA-UHFFFAOYSA-K 0.000 description 1
- 229940038472 dicalcium phosphate Drugs 0.000 description 1
- 229910000390 dicalcium phosphate Inorganic materials 0.000 description 1
- 150000004683 dihydrates Chemical class 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 238000013467 fragmentation Methods 0.000 description 1
- 238000006062 fragmentation reaction Methods 0.000 description 1
- IXCSERBJSXMMFS-UHFFFAOYSA-N hcl hcl Chemical compound Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 1
- 230000036571 hydration Effects 0.000 description 1
- 238000006703 hydration reaction Methods 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N hydrochloric acid Substances Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- GPRLSGONYQIRFK-UHFFFAOYSA-N hydron Chemical compound [H+] GPRLSGONYQIRFK-UHFFFAOYSA-N 0.000 description 1
- 235000019447 hydroxyethyl cellulose Nutrition 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- 235000019421 lipase Nutrition 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000002932 luster Substances 0.000 description 1
- 229910001425 magnesium ion Inorganic materials 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 230000002503 metabolic effect Effects 0.000 description 1
- 125000005341 metaphosphate group Chemical group 0.000 description 1
- 229920000609 methyl cellulose Polymers 0.000 description 1
- 239000001923 methylcellulose Substances 0.000 description 1
- 235000010981 methylcellulose Nutrition 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 229910052680 mordenite Inorganic materials 0.000 description 1
- 239000013618 particulate matter Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 235000010409 propane-1,2-diol alginate Nutrition 0.000 description 1
- 239000000770 propane-1,2-diol alginate Substances 0.000 description 1
- 235000013772 propylene glycol Nutrition 0.000 description 1
- 230000001698 pyrogenic effect Effects 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000035807 sensation Effects 0.000 description 1
- 235000019615 sensations Nutrition 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910002028 silica xerogel Inorganic materials 0.000 description 1
- 239000000344 soap Substances 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 description 1
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- AQMNWCRSESPIJM-UHFFFAOYSA-M sodium metaphosphate Chemical compound [Na+].[O-]P(=O)=O AQMNWCRSESPIJM-UHFFFAOYSA-M 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 101150035983 str1 gene Proteins 0.000 description 1
- 239000000271 synthetic detergent Substances 0.000 description 1
- 238000007669 thermal treatment Methods 0.000 description 1
- 230000036346 tooth eruption Effects 0.000 description 1
- UHVMMEOXYDMDKI-JKYCWFKZSA-L zinc;1-(5-cyanopyridin-2-yl)-3-[(1s,2s)-2-(6-fluoro-2-hydroxy-3-propanoylphenyl)cyclopropyl]urea;diacetate Chemical compound [Zn+2].CC([O-])=O.CC([O-])=O.CCC(=O)C1=CC=C(F)C([C@H]2[C@H](C2)NC(=O)NC=2N=CC(=CC=2)C#N)=C1O UHVMMEOXYDMDKI-JKYCWFKZSA-L 0.000 description 1
Classifications
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
- A61K8/19—Cosmetics or similar toiletry preparations characterised by the composition containing inorganic ingredients
- A61K8/26—Aluminium; Compounds thereof
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
- A61Q11/00—Preparations for care of the teeth, of the oral cavity or of dentures; Dentifrices, e.g. toothpastes; Mouth rinses
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K2800/00—Properties of cosmetic compositions or active ingredients thereof or formulation aids used therein and process related aspects
- A61K2800/40—Chemical, physico-chemical or functional or structural properties of particular ingredients
- A61K2800/41—Particular ingredients further characterized by their size
- A61K2800/412—Microsized, i.e. having sizes between 0.1 and 100 microns
Definitions
- This invention relates to improved dentifrice formulations.
- it involves the use of pH-modified synthetic and/or natural zeolites as multifunctional components for dentifrices.
- dentifrice since the dentifrice is for human use, it must be biologically compatible and safe for repeated use.
- dentifrices must be esthetically acceptable to the persons who will use them. Taste and texture must be pleasing and the dentifrice must not produce any unpleasant sensory perceptions. Organoleptic testing has shown that despite objective usefulness of a dentifrice, it will be rejected if its psycho-sensory effects are objectionable.
- Modern dentifrice compositions contain numerous components that have various therapeutic and cosmetic functions. Most of these compositions contain some sort of abrasive cleansing agent which aids in the removal of adherent deposits on the teeth. Particulate matter of specific hardness and certain particle size, shape and structure is utilized as such abrasives. These particles must also be compatible with other toothpaste ingredients and safe for repeated human use. Abrasives that are described in the patent literature and have found commercial application include silica xerogels, hydrated silicas, hydrated aluminas, calcium carbonate, dicalcium phosphate (anhydrous and dihydrate), calcium pyrophosphate and insoluble sodium metaphosphate. These agents are usually 2 to 30 ⁇ m in size. Products of about 10 ⁇ m appear to find the most commercial acceptance. Insoluble crystalline materials such as quartz have been found too abrasive for safe use on human dentition.
- dentifrice formulations contain a polishing or lustering agent in addition to the abrasive. These materials are generally softer and of smaller particle size than the abrasives. These agents are not useful in removing adherent stains and other material from the teeth; instead, they provide so-called luster to the teeth by a fine polishing action. Some of the agents used in this capacity include diatomaceous earth, pyrogenic and aerogel silicas and amorphous alumino-silicates. U.S. Pat. Nos. 3,911,104 and 4,036,949 disclose the use of amorphous alumino-silicates for such polishing agents. These materials have very high silica-to-alumina ratios and are not considered abrasives.
- a desirable ingredient for dentifrices is one that provides both abrasive and polishing actions.
- Such a dual-purpose material greatly simplifies the formulation and production of these multi-component products.
- Most abrasive particles must be ⁇ 10 ⁇ m or more in size to provide adequate action while particles of less than about 1 ⁇ m are required for polishing action.
- Producing particulate products with such bi-modal or wide range particle size distribution is difficult, expensive and is not done.
- Some silicas suggested as abrasives are crushed during use to provide particles of the correct size for polishing. The materials that provide sufficient crushed particles for good polishing often exhibit poor abrasion.
- Zeolites have been suggested as components in toothpastes and powders.
- Frank German Empire Patentschrift 378010
- Menkart and Ricciuti suggested (U.S. Pat. No. 3,250,680) the use of anhydrous zeolites in cosmetic preparations to produce a pleasant warm sensation on hydration during use. Their purpose was an esthetic satisfaction, rather than an objective use.
- Harth and Becker (U.S. Pat. No. 4,209,504) suggest the use of zeolites as a polishing agent in toothpaste. The main thrust of their invention is the use of zeolite as an agent with no corrosive effect on unlacquered aluminum surfaces. None of these inventions suggested the use of zeolite as an aid in control of dental caries.
- Kato et al. K. Kato, M. Shiba, Y. Okamoto, N. Nagata; Reports of the Institute for Medical and Dental Engineering I, 85: 1973 pointed out the compatibility of zeolites with fluoride ion, which is used as a caries preventive.
- crystallized metal alumino-silicates provide an array of functions when compounded into a dentifrice.
- Natural or synthetic zeolites of the correct particle size range function as abrasives and polishing agents.
- this dual functionality does not require a very wide particle distribution since the zeolites provide excellent abrasive action at particle sizes that are about an order of magnitude smaller than comparable prior art materials.
- Zeolites of such small size contribute the thickening action required for toothpaste.
- Therapeutic cations such as calcium, indium and stannous ions can be exchanged into the zeolite and added as an integral part of the abrasive.
- zeolites can be acid-modified without appreciably destroying their crystalline structure.
- authorities in the field state that strong acid will decompose zeolites (D. W. Breck; Zeolite Molecular Sieves; John Wiley and Sons; New York: 1974, p. 502 cf.) with either the formation of gel or with separation of insoluble silica without formation of gel.
- the specific result depends on the initial Al/Si in the starting zeolite. Only mordenite and clinoptilolite have been successfully treated with acid.
- Normally pH's of slurried zeolites are in the alkaline range; for example, a 10% slurry of Zeolite NaA has a pH of 10-10.5.
- a pH-modified zeolite can contribute to the maintenance of the proper pH in the oral environment, which will inhibit the formation of caries.
- zeolites can function as abrasives, lustering agents, thickeners, and carriers of ionic and non-ionic components.
- our multifunctional components for dentifrice compositions comprise various crystalline metallo alumino-silicates or mixtures thereof. These materials are also known as zeolites, and both natural and synthetic zeolites can be employed as our unique dentifrice component. We usually use synthetic zeolites since they are readily available and of consistent properties. U.S. Pat. Nos. 2,882,243-4; 3,012,853; 3,130,007 and 3,329,628 among many others describe zeolites that are suitable as well as methods for preparing them. While most zeolites can be employed according to our invention we usually use zeolites that conform to the following formula:
- x and y are integers; the mole ratio of x to y is in the range of 0.001 to 2.0 and Z is an integer from about 1 to 250.
- M is a metal and n is the valance of said metal.
- Zeolite Y can be useful.
- Such synthetic zeolites are most conveniently prepared by the thermal treatment of an alumino-silicate gel which is prepared by mixing aqueous sources of silica, alumina and alkali.
- the hydrothermal treatment causes the desired species to crystallize.
- Conventional filtering, washing, drying and deagglomeration steps complete the preparation.
- Synthetic zeolites are usually prepared in the sodium form while natural zeolites are rarely found in the sodium form. However, any desired metal form can be produced by proper ion exchange procedure.
- the zeolite can be completely or partially exchanged to achieve greater compatibility with other toothpaste ingredients or greater safety for repeated human use.
- the zeolite can be used as an ion carrier so that said ion can be added with the zeolite.
- Stannous, indium, calcium and magnesium ions among others can be added in this manner.
- Zeolites appear to be unique dentifrice abrasives in that they are effective even though they have a small ultimate particle size.
- Our zeolites are approximately an order of magnitude smaller than presently commercially acceptable abrasives that exhibit about the same or less abrasion. Since the zeolites are effective at such small sizes they also function as polishing or lustering agents without crushing or fragmentation.
- the small particle size and liquid absorbing capacity of our zeolite also enable it to thicken or provide good pasting properties when used in toothpastes.
- a single component that provides these three functionalities greatly simplifies formulation and manufacture of dentifrices.
- a unique use of the internal structure of zeolite involves enzymes which have been found to have beneficial effects in toothpastes as described in U.S. Pat. Nos. 4,058,595 and 4,082,841. These patents are hereby incorporated by reference as fully describing the enzymes which are used in combination with our zeolites.
- the enzymes employed are protase, carbohydrase or lipase. Mixtures of these materials are effective. These compounds require the presence of group IIA or IIB metal ions to enhance performance and provide stability.
- the incorporation of these materials in our zeolite is carried out as follows.
- the zeolite is provided in or ion-exchanged into the desired metal form, usually calcium or zinc.
- the zeolite is heated to remove the water from the pores and cages of the zeolite.
- the enzymes or mixture of enzymes are absorbed into the zeolite and incorporated into the dentifrice. This procedure assures a high enzyme activity on use.
- Humectants prevent hardness in the toothpaste and include, among others, glycerol, sorbitol and propylene glycol. Binders are important for obvious reasons and include gum tragacanth, sodium carboxymethylcellulose, methylcellulose, hydroxyethylcellulose, propylene glycol alginate, Indian gum, Irish moss, carrageenan, starch agar agar and the like. Other ingredients include soaps and synthetic detergents, flavoring agents such as sweeteners and oxygen releasers, buffers, preservatives and coloring agents.
- zeolites in dentifrice compositions require the use of a variety of zeolite types and a wide range of use levels in such compositions.
- the types of zeolites that are useful have been previously discussed.
- zeolites of the A and X structures are used.
- the calcium and sodium forms of these zeolites are most commonly used.
- very little of the zeolite (about 1% or so) may be formulated into the dentifrice.
- a dentifrice powder might contain well over 90% zeolite.
- we have found about 5 to 80% of a dentifrice can advantageously comprise a zeolite, a mixture of zeolites, an ion-exchanged zeolite, an impregnated zeolite or a mixture of all these types.
- zeolites with many metal ions are useful we have found that zeolites that have 20 to 100% of the metal sites exchanged with calcium, magnesium, or zinc appear to be the most useful. Zeolites exchanged to between 10 and 50% of the available exchange sites with stannous or indium ions provide useful therapeutic levels in dentifrice compositions.
- a zeolite can be prepared and utilized as a dentifrice composition.
- Zeolite NaA was prepared by hydrothermal treatment of an appropriate alumino-silicate gel. The particle size of this material averaged 2.8 ⁇ m. This material was tested as an abrasive and was found to have an RDA (radioactive dentin abrasion) value of 127.
- This zeolite was converted to Zeolite CaA by ion exchange. The zeolite was slurried in water and formed into a filter cake of about 3/8" on a vacuum filter. Then a solution of 0.1 N CaCl 2 in water was passed through the filter cake in 20 minutes.
- zeolite powders that had been pH-modified in the manner described above were subjected to re-exchange.
- 25 grams of the zeolite powder was dispersed in 200 ml of deionized water, and the slurry was adjusted to a pH of ⁇ 11 using ⁇ 5% NaOH. After filtering, the materials were washed with deionized water and air-dried.
- an additional step involving washing the filter cakes with a 500 ml solution of 10% CaCl 2 .2H 2 O was included.
- the crystallinity was measured by X-ray diffraction (XRD) is reported in Table IV.
- MHZ represents a zeolite with cation M and pH modification, for example, NaHA, sodium A zeolite which has been pH-modified as described above.
- zeolites The abrasive properties of zeolites are realized at very small average particle sizes. While most prior art abrasives are required in particle sizes up to 30 ⁇ m to realize their abrasive nature, the abrasive nature of zeolite is apparent in materials of particle sizes of 10 ⁇ m or less. We prefer zeolites of 5 ⁇ m or less with a lower limit of about 0.5 ⁇ m. A most preferred range is 0.5 to 3.5 for zeolites such as Zeolite NaHA, Zeolite CaHA, Zeolite NaHX and Zeolite CaHX. Some examples of zeolites and their abrasive action are summarized in the following table; calcium pyrophosphate is the standard, and the value therefor is 100.
- Toothpaste compositions that are formulated with zeolites and can accommodate water in the composition have the following compositions.
- composition to 100% consists of optional and cosmetic ingredients such as sweeteners, oxygen release agents, buffers, preservatives and coloring and flavoring agents.
- Toothpastes which contain a fluoride or enzyme source should be formulated with the following composition.
- the balance of the composition consists of optional and cosmetic ingredients such as sweeteners, oxygen release agents, buffers, preservatives and coloring agents. Water not associated with the other ingredients is not added to this composition.
- a toothpaste composition using zeolite as an abrasive/polishing agent having the following composition was prepared.
- This composition showed completely satisfactory abrasion and cleansing effects, and was personally acceptable.
- the Zeolite NaA described was ion-exchanged using a solution of CaCl 2 to provide Zeolite CaA wherein 93% of the available sodium was replaced by calcium.
- This material was pH-modified and substituted for the Zeolite NaHA in the composition described in Example 1. This composition exhibited satisfactory abrasion and cleansing effects and personal acceptability.
- the Zeolite CaHA as described in Example 2 was formulated into the following dentifrice.
- This composition shows zeolite as an abrasive, lustering agent, thickening agent and a carrier for stannous fluoride. The results are satisfactory.
- the zeolite of example 2 was formulated as follows:
- the zeolite of Example 2 was formulated as follows:
- Example 1 The NaHA of Example 1 was substituted for CaHA in Examples 3, 4 and 5.
- Zeolite NaHX Two samples of Zeolite NaHX are prepared with average particle sizes of 2.2 ⁇ m and 3.4 ⁇ m. Each of these materials is substituted for the Zeolite CaHA in the composition described in Example 3, 4 and 5, with satisfactory results.
- the sample of Zeolite NaX with a particle size of 2.2 ⁇ m is ion-exchanged to the calcium form using CaCl 2 solution. Over 90% of exchangeable sites are converted from sodium to calcium. This zeolite is pH-adjusted and substituted for Zeolite CaHA in Examples 3, 4 and 5 with satisfactory results.
- the Zeolite CaHX described in Example 8 is substituted for 1/3 (22 pbw) of the Zeolite CaHA in the composition described in Example 2.
- the zeolite composition is 22 pbw of Zeolite CaHX with completely satisfactory results.
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Abstract
Description
TABLE I ______________________________________ Hydrogen Ion Concentration (pH) Maximum Test Abrasive Test Value Dilution (w/w) ______________________________________ Insoluble sodium 4.2-5.4 1:10 metaphosphate Silica 4.6-5.1 1:10 Calcium pyrophosphate 4.4-5.1 1:10 ______________________________________
M.sub.x/n [(AlO.sub.2).sub.x (SiO.sub.2).sub.y ]ZH.sub.2 O
M.sub.12/n [(AlO.sub.2).sub.12 (SiO.sub.2).sub.12 ]ZH.sub.2 O
M.sub.85/n [(AlO.sub.2).sub.85 (SiO.sub.2).sub.107 ]ZH.sub.2 O
TABLE II ______________________________________ Properties of pH-Modified Zeolites Powders Final Crystal- Slurry LOI linity % By Wt. Acid pH (%) % XRD* Na.sub.2 O CaO ______________________________________ NaA H.sub.3 PO.sub.4 8.5 19.1 101 -- -- (Experimental) " 7.0 19.8 97 15.9 -- " 6.0 23.1 83 14.7 -- " 5.0 20.7 5 8.4 -- " 4.0 24.3 12 6.6 -- HCl 7.0 21.1 97 -- -- None 10.7 20.8 100 17.6 -- NaA None 11.0 20.4 94 18.2 -- (Commericial) H.sub.2 SO.sub.4 6.0 16.1 90 15.6 -- NaX H.sub.3 PO.sub.4 5.0 26.8 71 -- -- (Experimental) " 4.0 26.8 29 -- -- None 10.8 22.5 98 -- -- NaX None 10.2 22.8 103 15.3 -- (Commercial) H.sub.2 SO.sub.4 5.5 25.1 108 12.6 -- CaA H.sub.3 PO.sub.4 7.0 18.4 100 0.78 17.5 (Experimental) " 6.0 19.8 100 0.64 15.1 " 5.0 20.7 93 0.49 14.4 " 4.0 21.8 96 0.25 13.9 None 9.2 24.6 100* 0.78 14.4 ______________________________________ *Crystallinity measured against well characterized standards.
TABLE III __________________________________________________________________________ Chemical Analyses of pH-Modified Zeolites.sup.a,b Key Property NaHA CaHA NaHX CaHx __________________________________________________________________________ SiO.sub.2 (wt %) 33.2 32.0 33.4 37.1 37.2 35.7 Al.sub.2 O.sub.3 (wt %).sup.c 28.9 29.6 30.2 26.2 26.7.sup.d 25.3 Na.sub.2 O (wt %) 16.0 2.2 4.5 13.1 9.1 5.4 CaO (wt %) -- 13.8 11.5 -- -- 8.2 H.sub.2 O (wt % by LOI) 21.9 22.4 20.4 23.6 27.0 25.4 Totals 100.0 100.0 100.0 100.0 100.0 100.0 Si/Al Atom Ratio 0.97 0.92 0.94 1.20 1.18 1.20 Slurry pH (5% sol. in 6.8/-- 9.2/7.3 8.4/7.5 -- 7.0/6.0 6.3/6.0 D°.I. H.sub.2 O/in .1N NaCl sol) Meq Na.sup.+ (anhydrous) 6.61 0.92 1.82 5.53 4.02 2.34 Meq Ca.sup.++ (anhydrous).sup.e -- 6.34 5.15 -- -- 3.92 Meq H.sub.2 O (anhydrous) 0.77 0.12 0.41 0.86 2.37 0.14 ##STR1## 10/10 2/88 6/75 13/13 37/37 2/63 __________________________________________________________________________ .sup.a Commerical NaA used as starting material. .sup.b Commerical NaX used as starting material. .sup.c Determined by difference. .sup.d Determined by analytical methods. .sup.e Determined by difference; total sodium as reported in Table II.
TABLE IV ______________________________________ Crystallinity of pH-Modified Zeolites.sup.a Crystallinity (% XRD).sup.b Na--A CaA Na--X CaX ______________________________________ Initial Material 94 --.sup.a 103 --.sup.a After pH Modification 90 81 108 109 After pH Modification 94 89 109 109 and Back-Exchange.sup.c Lowest Slurry pH During 5.9 5.9 5.4 5.4 Modification ______________________________________ .sup.a Commercial Na--A and commercial NaX zeolites were used as the starting materials, respectively, for these samples. .sup.b Moisture contents (LOI) of all samples are in the range that does not affect XRD measurements. .sup.c Back-exchange procedure described in text.
TABLE V ______________________________________ Radioactive Dentin Abrasion Values for Zeolites and Prior Art Materials Average Particle RDA Abrasive Agent Size (μm) Value ______________________________________ Calcium Pyrophosphate -- 100 Prior Art Silica Xerogel 8.0 117 Experimental Zeolite NaHA 2.8 127 Experimental Zeolite NaHA 4.6 166 Experimental Zeolite CaHA 2.8 117 Commercial Zeolite NaA 6.6 166 Commercial Zeolite NaA 4.2 174 Commercial Zeolite NaA 3.0 110 Experimental Zeolite NaHX 3.4 154 ______________________________________
______________________________________ General Preferred ______________________________________ Zeolite (% by weight) 5-80 10-65 Humectant (% by weight) 10-75 15-55 Water (% by weight) 10-50 15-45 Sodium Lauryl Sulfate/Glycerin* 3-10 3-10 Binder 2-5 2-5 ______________________________________ *Mixture consists of 79% Sodium Lauryl Sulfate and 21% glycerin.
______________________________________ General Preferred ______________________________________ Zeolite (% by weight) 5-80 10-65 Humectant 10-90 15-75 Sodium Lauryl Sulfate/Glycerin* 3-15 3-15 Binder 2-7 2-7 Flavorant and Colorant 0.5-4 0.5-2 Fluoride or Enzyme Source 0.05-0.75 .2-.75 ______________________________________ *Mixture consists of 79% Sodium Lauryl Sulfate and 21% glycerin.
______________________________________ Zeolite NaHA (2.8 μm average particle size) 44.0 pbw Sorbitol Syrup (70% in water) 35.0 pbw NaCMC 0.3 pbw Stannous Fluoride 0.4 pbw 21% Sodium Lauryl Sulfate/79% Glycerin 12.0 pbw Saccharin 0.2 pbw Coloring Agents 0.2 pbw Flavorants 0.2 pbw Water To 100 pbw ______________________________________
______________________________________ Zeolite CaHA 41.0 pbw Sorbitol Syrup 44.0 pbw 21% Sodium Lauryl Sulfate/79% Glycerin 15.8 pbw Saccharin 0.2 pbw Colorant 0.5 pbw Flavorant 0.2 pbw Stannous Fluoride 0.03 pbw Water To 100 pbw ______________________________________
______________________________________ Zeolite CaHA 41.0 pbw Sorbitol Syrup 44.0 pbw 21% Sodium Lauryl Sulfate/79% Glycerin 15.8 pbw Saccharin 0.2 pbw Colorant 0.5 pbw Flavorant 0.2 pbw Sodium Fluoride 0.02 pbw Water To 100 pbw ______________________________________
______________________________________ Zeolite CaHA 41.0 pbw Sorbitol Syrup 44.0 pbw 21% Sodium Lauryl Sulfate/79% Glycerin 15.8 pbw Saccharin 0.2 pbw Colorant 0.2 pbw Flavorant 0.2 pbw Sodium Monofluorophosphate 0.04 pbw Water To 100 pbw ______________________________________
Claims (5)
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US6812979A | 1979-08-20 | 1979-08-20 | |
US06/217,602 US4349533A (en) | 1979-08-20 | 1980-12-18 | Toothpaste containing pH-adjusted zeolite |
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Cited By (27)
Publication number | Priority date | Publication date | Assignee | Title |
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FR2516382A1 (en) * | 1981-11-19 | 1983-05-20 | Colgate Palmolive Co | STABLE TOOTHPASTE CONTAINING SILICAOUS ACID POLISHING AGENT |
FR2516383A1 (en) * | 1981-11-19 | 1983-05-20 | Colgate Palmolive Co | STABLE TOOTHPASTE CONTAINING SILENT NEUTRAL POLISHING AGENT |
US4460565A (en) * | 1981-07-03 | 1984-07-17 | Intradal N.V. | Anticariogenic remineralizing dentifrice |
FR2540093A1 (en) * | 1983-02-02 | 1984-08-03 | Rhone Poulenc Spec Chim | Process for the preparation of an alkaline silicoaluminate which can be used in dentifrice compositions (toothpastes) |
US4537764A (en) * | 1981-08-13 | 1985-08-27 | Laclede Professional Products, Inc. | Stabilized enzymatic dentifrice containing B-D-glucose and glucose oxidase |
US4582701A (en) * | 1984-05-11 | 1986-04-15 | Colgate-Palmolive Company | Anhydrous dentifrice |
US4592855A (en) * | 1984-11-16 | 1986-06-03 | Union Carbide Corporation | Effervescent compositions |
EP0187912A2 (en) * | 1985-01-14 | 1986-07-23 | PQ Corporation | Personal care products |
US4627972A (en) * | 1984-11-16 | 1986-12-09 | Union Carbide Corporation | Effervescent dentifrice |
EP0297563A2 (en) * | 1987-06-30 | 1989-01-04 | Uop | Anticariogenic and anticalculus compositions containing zeolitic zinc cations |
US4818518A (en) * | 1984-11-16 | 1989-04-04 | Uop | Effervescent dentifrice |
EP0394948A2 (en) * | 1989-04-24 | 1990-10-31 | Kanebo Ltd. | Stabilized synthetic zeolite and a process for the preparation thereof |
US5094839A (en) * | 1990-11-09 | 1992-03-10 | Abrasive Technology, Inc. | Abrasive polishing composition |
US5443812A (en) * | 1989-04-24 | 1995-08-22 | Kanebo Ltd. | Stabilized synthetic zeolite and a process for the preparation thereof |
US5958871A (en) * | 1995-09-26 | 1999-09-28 | The Procter & Gamble Company | Detergent composition based on zeolite-bicarbonate builder mixture |
US6123925A (en) * | 1998-07-27 | 2000-09-26 | Healthshield Technologies L.L.C. | Antibiotic toothpaste |
US20030118518A1 (en) * | 1999-04-11 | 2003-06-26 | Rainer Hahn | Suspension for the treatment of natural hard tissue and method of treatment |
US20030138384A1 (en) * | 2000-01-21 | 2003-07-24 | The Procter & Gamble Co. | Methods of using a beverage composition |
US20040047815A1 (en) * | 2000-12-20 | 2004-03-11 | Bonals Ana Torrado | Dentifrice product |
WO2004091564A1 (en) * | 2003-04-17 | 2004-10-28 | Robert Basic | Oral composition for stabilization,(re)calcification and (re)mineralization of tooth enamel and dentine |
US20050048090A1 (en) * | 2003-09-03 | 2005-03-03 | Rau Allen H. | Temperature changing skin care product |
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Cited By (36)
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US4460565A (en) * | 1981-07-03 | 1984-07-17 | Intradal N.V. | Anticariogenic remineralizing dentifrice |
US4537764A (en) * | 1981-08-13 | 1985-08-27 | Laclede Professional Products, Inc. | Stabilized enzymatic dentifrice containing B-D-glucose and glucose oxidase |
FR2516382A1 (en) * | 1981-11-19 | 1983-05-20 | Colgate Palmolive Co | STABLE TOOTHPASTE CONTAINING SILICAOUS ACID POLISHING AGENT |
FR2516383A1 (en) * | 1981-11-19 | 1983-05-20 | Colgate Palmolive Co | STABLE TOOTHPASTE CONTAINING SILENT NEUTRAL POLISHING AGENT |
FR2540093A1 (en) * | 1983-02-02 | 1984-08-03 | Rhone Poulenc Spec Chim | Process for the preparation of an alkaline silicoaluminate which can be used in dentifrice compositions (toothpastes) |
US4582701A (en) * | 1984-05-11 | 1986-04-15 | Colgate-Palmolive Company | Anhydrous dentifrice |
US4592855A (en) * | 1984-11-16 | 1986-06-03 | Union Carbide Corporation | Effervescent compositions |
US4627972A (en) * | 1984-11-16 | 1986-12-09 | Union Carbide Corporation | Effervescent dentifrice |
US4818518A (en) * | 1984-11-16 | 1989-04-04 | Uop | Effervescent dentifrice |
EP0187912A2 (en) * | 1985-01-14 | 1986-07-23 | PQ Corporation | Personal care products |
US4626550A (en) * | 1985-01-14 | 1986-12-02 | Pq Corporation | Zeolite for personal care products |
EP0187912A3 (en) * | 1985-01-14 | 1987-09-23 | Pq Corporation | Zeolite for personal care products |
EP0297563A2 (en) * | 1987-06-30 | 1989-01-04 | Uop | Anticariogenic and anticalculus compositions containing zeolitic zinc cations |
US4826676A (en) * | 1987-06-30 | 1989-05-02 | Uop | Anticariogenic and anticalculus compositions containing zeolitic zinc cations |
EP0297563A3 (en) * | 1987-06-30 | 1989-09-20 | Union Carbide Corporation | Anticariogenic and anticalculus compositions containing zeolitic zinc cations |
EP0394948A3 (en) * | 1989-04-24 | 1992-07-29 | Kanebo Ltd. | Stabilized synthetic zeolite and a process for the preparation thereof |
EP0394948A2 (en) * | 1989-04-24 | 1990-10-31 | Kanebo Ltd. | Stabilized synthetic zeolite and a process for the preparation thereof |
US5443812A (en) * | 1989-04-24 | 1995-08-22 | Kanebo Ltd. | Stabilized synthetic zeolite and a process for the preparation thereof |
US5094839A (en) * | 1990-11-09 | 1992-03-10 | Abrasive Technology, Inc. | Abrasive polishing composition |
WO1992008437A1 (en) * | 1990-11-09 | 1992-05-29 | Abrasive Technology, Inc. | Abrasive polishing composition viscous carrier |
US5958871A (en) * | 1995-09-26 | 1999-09-28 | The Procter & Gamble Company | Detergent composition based on zeolite-bicarbonate builder mixture |
US6123925A (en) * | 1998-07-27 | 2000-09-26 | Healthshield Technologies L.L.C. | Antibiotic toothpaste |
US7276229B1 (en) | 1998-09-09 | 2007-10-02 | Smithkline Beecham P.L.C. | Oral compositions comprising a viscosity modifier for reduction of tooth erosion |
US20030118518A1 (en) * | 1999-04-11 | 2003-06-26 | Rainer Hahn | Suspension for the treatment of natural hard tissue and method of treatment |
US20030138384A1 (en) * | 2000-01-21 | 2003-07-24 | The Procter & Gamble Co. | Methods of using a beverage composition |
US6984376B2 (en) | 2000-01-21 | 2006-01-10 | Procter & Gamble | Methods of inhibiting dental erosion/discoloration using a beverage composition comprising a long chain polyphosphate |
US9585827B2 (en) | 2000-01-21 | 2017-03-07 | The Procter & Gamble Company | Kits comprising a beverage composition and information for use |
US20050245388A1 (en) * | 2000-06-02 | 2005-11-03 | Ineos Silicas Limited | Zeolite compositions and their use |
US20040047815A1 (en) * | 2000-12-20 | 2004-03-11 | Bonals Ana Torrado | Dentifrice product |
WO2004091564A1 (en) * | 2003-04-17 | 2004-10-28 | Robert Basic | Oral composition for stabilization,(re)calcification and (re)mineralization of tooth enamel and dentine |
US20060088480A1 (en) * | 2003-04-17 | 2006-04-27 | Robert Basic | Oral composition for stabilization, (re)calcification and (re)mineralization of tooth enamel and dentine |
US20050048090A1 (en) * | 2003-09-03 | 2005-03-03 | Rau Allen H. | Temperature changing skin care product |
US20070292458A1 (en) * | 2004-01-09 | 2007-12-20 | Ineos Silicas Limited | Dentifrice Compositions Containing Zeolites |
US20080132438A1 (en) * | 2006-11-30 | 2008-06-05 | Kimberly-Clark Worldwide, Inc. | Cleansing composition incorporating a biocide, heating agent and thermochromic substance |
US8318654B2 (en) | 2006-11-30 | 2012-11-27 | Kimberly-Clark Worldwide, Inc. | Cleansing composition incorporating a biocide, heating agent and thermochromic substance |
US11253444B2 (en) * | 2016-06-24 | 2022-02-22 | Colgate-Palmolive Company | Oral care composition |
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